Bi aliovalent substitution in Li7La3Zr2O12 garnets: Structural and ionic conductivity effects

Schwanz, Derek K.; Villa, Andres; Balasubramanian, Mahalingam; Helfrecht, Benjamin A.; Marinero, Ernesto E.

doi:10.1063/1.5141764

Title: Bi aliovalent substitution in Li₇La₃Zr₂O₁₂ garnets: Structural and ionic conductivity effects

Journal Article · Mon Mar 02 00:00:00 EST 2020 · AIP Advances

DOI:https://doi.org/10.1063/1.5141764· OSTI ID:1647159

Schwanz, Derek K. ^[1]; Villa, Andres ^[1];

^[2];

^[1];

^[1]

Purdue Univ., West Lafayette, IN (United States)
Argonne National Lab. (ANL), Argonne, IL (United States)

We report on the synthesis of cubic-phase garnet-type solid-state electrolytes based on Bi-doped Li₇La₃Zr₂O₁₂ (LLZO). Bi aliovalent substitution of Zr in LLZO utilizing the Pechini processing method is employed to synthesize Li_7-xLa₃Zr_2-xBi_xO₁₂ compounds. A strong dependence of the ionic conductivity on Bi content is observed, and under our synthesis and sintering conditions, a >100-fold increase over the un-doped sample is observed for x=0.75. Cubic-phase Li₆La₃Zr₁BiO₁₂ compounds are generated upon annealing in air in the temperature range 650 °C-900 °C. In contrast, in the absence of Bi, the cubic garnet phase of Li₇La₃Zr₂O₁₂ is not formed below 700 °C and a transformation to the tetragonal phase is observed at similar to 900 °C for this un-doped compound. The role of Bi in lowering the formation temperature of the garnet cubic phase and in the ionic conductivity improvements is investigated in this work. We ascribe the effect of Bi-doping on ionic conductivity increments to changes in Li⁺-site occupancy and lattice parameters and the reduction in the formation temperature for the cubic-phase formation to rate enhancements of the solid-state reaction. To identify the site occupancy of Bi in the garnet structure, we employ synchrotron extended x-ray absorption fine structure spectroscopy. Our results indicate that Bi additions occupy the Zr-type sites exclusively, to within the accuracy of the measurements.

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Research Organization:: Argonne National Lab. (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Joint Center for Energy Storage Research (JCESR)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1647159

Alternate ID(s):: OSTI ID: 1602333

Journal Information:: AIP Advances, Vol. 10, Issue 3; ISSN 2158-3226

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 11 works

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Title: Bi aliovalent substitution in Li7La3Zr2O12 garnets: Structural and ionic conductivity effects

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Title: Bi aliovalent substitution in Li₇La₃Zr₂O₁₂ garnets: Structural and ionic conductivity effects